Copolyesters of iso- or terephthalic acid, ethylene glycol, 1,3 bis(2-hydroxyethoxy) benzene, and possibly other diols, have lower 0.sub.2 and CO.sub.2 permeabilities because of the 1,3 bis(2-hydroxyethoxy) benzene reactant. Also disclosed are hollow containers, sheet and film made from such copolyesters.

Description

12 parts

›This invention relates to copolyesters based on terephthalic…

This invention relates to copolyesters based on terephthalic or isophthalic acids or both, which contain 1,3 bis(2-hydroxyethoxy)benzene as one of the diol reactants in order to prepare solid copolyesters having lower oxygen and carbon dioxide permeabilities than without such co-reactant.

Polyesters based on terephthalic acid and ethylene glycol and copolyesters based on isophthalic acid and ethylene glycol are well known for making containers and packaging materials such as film and sheet. When terephthalic acid is used as the acid reactant, the polymer is highly crystallizable, which is highly desirable for many applications. When isophthalic acid is used, the polymer is only difficulty crystallizable, if at all, and also has a somewhat lower glass transition temperature than when terephthalic acid is used. It is also currently more expensive.

Another important property for many packaging applications is low permeability to gases such as carbon dioxide and oxygen. Both polymers are satisfactory in this respect for many packaging applications, but for applications where a very low permeability is required, isophthalic acid can be chosen because it is much less permeable when polymerized with ethylene glycol than is terephthalic acid, particularly if the application does not require a crystallizable polymer. Of course, any mixture of the two acids can be used to make a copolyester, and such copolyesters have intermediate properties. With any of the foregoing polymers, it is often desirable to lower the carbon dioxide and oxygen permeabilities by suitable modification.

I have now discovered that the oxygen and carbon dioxide permeabilities of such polyesters can be lowered by replacing part of the diol with 1,3 bis(2-hydroxyethoxy)benzene.

Thus, according to one aspect of the present invention there is provided a solid thermoplastic copolyester consisting essentially of the polymeric reaction product of:

(A) reactant(s) selected from isophthalic acid, terephthalic acid, and their C 1 to C 4 alkyl esters, and any mixture thereof in any proportion,

(B) reactants, 1,3 bis(2-hydroxyethoxy)benzene plus ethylene glycol, and optionally one or more other ester forming dihydroxy organic hydrocarbon reactant(s), and, optionally,

(1) the amount of said 1,3 bis(2-hydroxyethoxy)benzene is 5-90, usually not less than 10 or more than 80, mol percent of the amount of A reactants,

(2) the combined amount of B and C reactants is about 110 to 300 mol percent of the amount of A reactants,

(3) the amount of said other ester forming dihydroxy organic hydrocarbon reactant(s) is zero to 20, usually zero to 15, mol percent of the amount of said A reactants, and

(4) the combined amount of said (C) reactant plus said 1,3 bis(2-hydroxyethoxy)benzene and said other ester forming dihydroxy organic hydrocarbon reactant(s) is not over 90 mol percent of said A reactants.

In the foregoing copolyesters the optional C reactant, bis(4-β-hydroxyethoxyphenyl) sulfone, is used when it is necessary to raise the glass transition temperature of the composition for a particular application or use.

When less than 5 mol percent of 1,3 bis(2-hydroxyethoxy) benzene is used, the effect on permeabilities is not as significant as desired. When over 90 mol percent is used, the reaction or polycondensation rate is lower than desired.

When it is stated herein that the reactants "consist essentially of" certain reactants, this means that the reactants positively recited are essential, but that the usual other ingredients can be included, such as colorants, inert fillers, polymerization catalysts, cross-linking agents to improve melt strength (see my U.S. Pat. No. 4,188,357, issued Feb. 12, 1980, and U.S. Pat. No. 4,307,060 issued Dec. 22, 1981, wherein from 0.1 to 0.7 mol percent of trimellitic acid anhydride, trimesic acid, or a triol,RC(CH 2 OH) 3 , where R is methyl or ethyl, is included to increase melt strength). Such other ingredients can be included if they do not deleteriously affect the basic and novel characteristics of the products of my invention or of the process of the present invention, as they are described herein.

The copolyesters of the invention are solid copolyesters having an inherent viscosity of at least 0.4 dl/g., usually at least 0.5 and for most commercial applications, at least 0.7 dl/g. The inherent viscosities referred to herein are those measured at 25° C., using a solution of 0.25 gms. of polymer dissolved in 100 milliliters of a mixture of 3 weight parts phenol with 2 weight parts 1,1,2,2 tetrachloro-ethane.

In the following illustrative examples and in the claims, the oxygen and carbon dioxide permeabilities refer to the determinations made on substantially unoriented pressed films.

The glass transition temperature, Tg, was determined using a Perkin-Elmer Differential Scanning Calorimeter, Model DSC-2, in a manner similar to that described in U.S. Pat. No. 3,822,322, issued July 2, 1974, using a heating rate of 10° C./minute.

›Examples11

›EXAMPLE 1

Into a 1-liter stainless steel reactor equipped with a storer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

233 g dimethyl terephthalate

167.6 g ethylene glycol

59.4 g 1,3 bis(2-hydroxyethoxy)benzene

0.0660 g titanyl acetylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.0303 g manganese hypophosphite monohydrate

0.0114 g tetrasodium ethylenediaminetetraacetate

0.4325 g 1,1,1 tris hydroxymethyl ethane

______________________________________

The reaction mixture was heated at 200° C. for 1 hour and 20 minutes under nitrogen atmosphere. Methanol was continuously distilled out during this period. Then 0.4128 g of tris(nonylphenyl)phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 1 hour under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 275° C. under less than 0.4 mm Hg for 2 hours, 50 minutes. The copolyester has an inherent viscosity of 0.86 dl/g. The glass transition temperature was 72° C. The O 2 and CO 2 gas permeabilities were 5.9 and 35.8 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 2

Poly(ethylene terephthalate) was prepared as follows:

Into a 500 ml 3-necked round bottom flask, equipped with a nitrogen gas inlet tube, stirrer and a condenser, the following compounds were added:

______________________________________

46.5 g dimethyl terephthalate

35.4 g ethylene glycol

0.0263 g zinc acetate dihydrate

0.01398 g antimony trioxide

______________________________________

The contents of the flask were heated at 220° C. under nitrogen atmosphere for 3 hours. During this time, methanol was distilled off. Then the reaction temperature was raised to 280° C., nitrogen flow was stopped and vacuum was gradually applied until less than 0.5 mm Hg. Excess ethylene glycol was continuously distilled off. The reaction was stopped after 4 hours. The inherent viscosity was 0.83, the glass transition temperature was 72° C., the oxygen permeability was 8.5 cc.·mil/100 in. 2 ·day·atm. and the carbon dioxide permeability was 55.3 cc.·mil/100 in. 2 ·day·atm.

›EXAMPLE 3

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

233.0 g dimethyl terephthalate

134.1 g ethylene glycol

166.3 g 1,3 bis(2-hydroxyethoxy)benzene

0.4325 g 1,1,1 tris(hydroxymethyl)ethane

0.0114 g titanyl acetylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.0114 g tetrasodium ethylenediaminetetraacetate

0.0303 g manganese hypophosphite monohydrate

______________________________________

The reaction mixture was heated at 200° C. for 1 hour under nitrogen atmosphere. Methanol was continuously distilled out during this period. Then 0.4128 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 55 minutes under nitrogen atmosphere. Then the nitrogen gas flow was applied. The reaction was continued at 270° C. under less than 0.4 mm Hg for 51/2 hours. The copolyester had an inherent viscosity of 0.65. The glass transition temperature was 64° C. The O 2 and CO 2 gas permeabilities were 3.8 and 22.4 cc·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 4

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

332.3 g isophthalic acid

192.2 g ethylene glycol

19.8 g 1,3 bis(2-hydroxyethoxy)benzene

0.1100 g titanyl acetylacetonate

0.1458 g Sb.sub.2 O.sub.3

0.0190 g tetrasodium ethylenediaminetetraacetate

0.7209 g 1,1,1 tris(hydroxymethyl)ethane

______________________________________

The reaction mixture was heated at 220° C. for 1 hour, and then at 240° C. for 40 minutes under nitrogen atmosphere. Water was continuously distilled out during this period. Then 0.688 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 50 minutes under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 270° C. under less than 0.4 mm Hg for 3 hours, 55 minutes. The copolyester had an inherent viscosity of 0.83. The glass transition temperature was 61° C. The O 2 and CO 2 gas permeabilities were 1.6 and 7.1 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 5

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

332.3 g isophthalic acid

180 g ethylene glycol

59.4 g 1,3 bis(2-hydroxyethoxy)benzene

0.7209 g 1,1,1 tris(hydroxymethyl)ethane

0.1100 g titanyl acetylacetonate

0.1458 g Sb.sub.2 O.sub.3

0.019 g tetrasodium ethylenediaminetetraacetate

______________________________________

The reaction mixture was heated at 220° C. for 1 hour, and then at 240° C. for 30 minutes under nitrogen atmosphere. Water was continuously distilled out during this period. Then 0.688 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 40 minutes under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 270° C. under less than 0.4 mm Hg for 41/2 hours. The copolyester had an inherent viscosity of 0.82. The glass transition temperature was 60° C. The O 2 and CO 2 gas permeabilities were 1.6 and 6.6 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 6

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

139.5 g isophthalic acid

59.8 g terephthalic acid

107.9 g ethylene glycol

35.6 g 1,3 bis(2-hydroxyethoxy)benzene

0.4325 g 1,1,1 tris(hydroxymethyl)ethane

0.066 g titanylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.0114 g tetrasodium ethylenediaminetetraacetate

0.0303 g manganese hypophosphite monohydrate

______________________________________

The reaction mixture was heated at 220° C. for 1 hour, and then at 240° C. for 25 minutes under nitrogen atmosphere. Water was continuously distilled out during this period. The 0.1862 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 35 minutes under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 275° C. under less than 0.4 mm Hg for 4 hours, 5 minutes. The copolyester has an inherent viscosity of 0.89. The glass transition temperature was 63° C. The O 2 and CO 2 gas permeabilities were 2.0 and 9.7 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 7

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

139.5 g isophthalic acid

59.8 g terephthalic acid

100.4 g ethylene glycol

35.6 g 1,3 bis(2-hydroxyethoxy)benzene

40.6 g bis(4-β-hydroxyethoxyphenyl)sulfone

0.4325 g 1,1,1 tris(hydroxymethyl)ethane

0.0660 g titanylacetylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.0114 g tetrasodium ethylenediaminetetraacetate

0.0303 g manganese hypophosphite monohydrate

______________________________________

The reaction mixture was heated at 200° C. for 20 minutes, and then at 240° C. for 50 minutes under nitrogen atmosphere. Water was continuously distilled out during this period. Then 0.4128 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 25 minutes under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 270° C. under less than 0.4 mm Hg for 4 hours. The copolyester had an inherent viscosity of 0.77. The glass transition temperature was 72° C. The O 2 and CO 2 gas permeabilities were 2.5 and 12.9 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 8

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

139.5 g isophthalic acid

59.8 g terephthalic acid

100.4 g ethylene glycol

35.6 g 1,3 bis(2-hydroxyethoxy)benzene

17.3 g 1,4 trans cyclohexanedimethanol

0.0660 g titanylacetylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.0114 g tetrasodium ethylenediaminetetraacetate

0.0303 g manganese hypophosphite monohydrate

0.4325 g 1,1,1 tris(hydroxymethyl)ethane

______________________________________

The reaction mixture was heated at 200° C. for 1 hour, and then at 240° C. for 1 hour under nitrogen atmosphere. Water was continuously distilled out during this period. Then 0.4128 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 30 minutes under nitrogen atmosphere. Then the nitrogen gas glow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 270° C. under less than 0.4 mm Hg for 4 hours. The copolyester had an inherent viscosity of 0.81. The glass transition temperature was 63° C. The O 2 and CO 2 gas permeabilities were 3.3 and 15.3 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 9

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

139.5 g isophthalic acid

59.8 g terephthalic acid

78.2 g ethylene glycol

35.6 g 1,3 bis(2-hydroxyethoxy)benzene

12.5 g neopentyl glycol

0.4325 g 1,1,1 tris(hydroxymethyl)ethane

0.0660 g titanyl acetylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.0114 g tetrasodium ethylenediaminetetraacetate

0.0303 g manganese hypophosphite monohydrate

______________________________________

The reaction mixture was heated at 240° C. for 1 hour under 35 psi nitrogen atmosphere, and then the pressure was lowered to atmospheric. Water was continuously distilled out during this period. Then 0.4128 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 20 minutes under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 270° C. under less than 0.4 mm Hg for 4 hours. The copolyester had an inherent viscosity of 0.90. The glass transition temperature was 65° C. The O 2 and CO 2 gas permeabilities were 3.0 and 10.2 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 10

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

179.4 g isophthalic acid

19.9 g terephthalic acid

78.2 g ethylene glycol

35.6 g 1,3 bis(2-hydroxyethoxy)benzene

17.8 g diethylene glycol

0.0660 g titanyl acetylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.4325 g 1,1,1 tris(hydroxymethyl)ethane

0.0114 g tetrasodium ethylenediaminetetraacetate

0.0303 g manganese hypophosphite monohydrate

______________________________________

The reaction mixture was heated at 240° C. for 1 hour under 35 psi nitrogen atmosphere, and then the pressure was lowered to atmospheric. Water was continuously distilled our during this period. Then 0.4128 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 20 minutes under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 270° C. under less than 0.4 mm Hg for 5 hours. The copolyester had an inherent viscosity of 0.84. The glass transition temperature was 59° C. The O 2 and CO 2 gas permeabilities were 2.3 and 11.3 cc.·mil/100 in. 2 ·day·atm., respectively.

›EXAMPLE 11

Into a 1-liter stainless steel reactor equipped with a stirrer, nitrogen gas inlet port and a condenser, the following were added:

______________________________________

199.3 g isophthalic acid

89.4 g ethylene glycol

213.8 g 1,3 bis(2-hydroxyethoxy)benzene

0.4325 g 1,1,1 tris(hydroxymethyl)ethane

.0660 g titanyl acetylacetonate

0.0874 g Sb.sub.2 O.sub.3

0.0114 g tetrasodium ethylenediaminetetraacetate

0.0303 g manganese hypophosphite monohydrate

______________________________________

The reaction mixture was heated at 200° C. for 1/2 hour, and then at 240° C. for 1 hour under nitrogen atmosphere. Water was continuously distilled out during this period. Then 0.4128 g of tris (nonylphenyl) phosphite was added to the mixture in the reactor. The reaction temperature was increased to 250° C. and maintained for 40 minutes under nitrogen atmosphere. Then the nitrogen gas flow was stopped and a vacuum of less than 0.4 mm Hg was applied. The reaction was continued at 275° C. under less than 0.4 mm Hg for 51/2 hours. The copolyester had an inherent viscosity of 0.45.

As noted, the solid copolyesters of the invention are contemplated as especially useful in packaging applications because of their combination of properties, including permeabilities, such as in making hollow containers and film and sheet useful for packaging. Thus, another aspect of the invention contemplates such products made of such copolyesters. Such containers may be made by blow molding or by injection molding, or by other known processes.

As will be evident to those skilled in the art, various modifications of this invention can be made or followed in the light of the foregoing disclosure and discussion without departing from the spirit and scope of the disclosure or from the scope of the claims.

As used herein and in the claims the recited "ester forming dihydroxy organic hydrocarbon reactants" means simple hydrocarbons wherein two hydrogens bonded to two C atoms are replaced by hydroxyl groups; and also similarly hydroxylated oxyhydrocarbons, i.e., ethers, wherein carbon atoms are connected by --0-- bonds. For instance, the diethylene glycol of Example 10 is included in the term. The term of course excludes compounds containing other than C, H and O atoms.

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Claims

7 · 1 independent · depth 3

7 granted claims

›1.independentA solid thermoplastic copolyester consisting essentially of the polymeric reaction product of (A) reactant(s) selected from isophthalic acid, terephth…+6

Classifications

10 codes

IPC · International Patent Classification

Section C — Chemistry; metallurgy

C08G63/199
C08G63/688
C08G63/00
C08G63/68
C08G63/66

USPC · US Patent Classification

528/173528/193528/176528/194528/195

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Lester L. Lee

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Office	Publication	Kind	Published	Filed	Status	Title
USthis patent	US-4398017-A	A	9 Aug 1983	9 Mar 1982	granted	Copolyesters
JP	JP-S58167617-A	A	3 Oct 1983	24 Jan 1983	published	Copolyester
JP	JP-S6340444-B2	B2	11 Aug 1988	24 Jan 1983	published	no title held

›Other offices — 12 members

Office	Publication	Kind	Published	Filed	Status	Title
AU	AU-1000283-A	A	29 Sep 1983	4 Jan 1983	published	Copolyester
AU	AU-537533-B2	B2	28 Jun 1984	4 Jan 1983	granted	Copolyester
BR	BR-8301126-A	A	22 Nov 1983	8 Mar 1983	published	Copoliester termoplastico solido,bem como recipientes ocos e folha ou filme formados com tal copoliesterpt
CA	CA-1183640-A	A	5 Mar 1985	21 Dec 1982	granted	Copolyestersfr
DE	DE-3306645-A1	A1	15 Sep 1983	25 Feb 1983	published	Fester thermoplastischer copolyester und verpackungsmaterialien darausde
DE	DE-3306645-C2	C2	1 Jun 1989	25 Feb 1983	granted	no title held
FR	FR-2523139-A1	A1	16 Sep 1983	8 Feb 1983	published	Copolyesters et leurs applicationsfr
FR	FR-2523139-B1	B1	5 Jul 1985	8 Feb 1983	granted	Copolyesters et leurs applicationsfr
GB	GB-8305546-D0	D0	30 Mar 1983	1 Mar 1983	published	Copolyesters
GB	GB-2116188-A	A	21 Sep 1983	1 Mar 1983	published	Copolyesters
GB	GB-2116188-B	B	29 Oct 1986	1 Mar 1983	granted	Copolyesters
ZA	ZA-83141-B	B	29 Feb 1984	10 Jan 1983	published	Copolyesters

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